Composite and reinforced coatings on proppants and particles

ABSTRACT

A high strength particle comprised of a particulate substrate, a substantially cured inner resin coating, an outer resin coating, and a reinforcing agent interspersed at the inner coating/outer coating boundary.

The present invention relates to resin coated particles, their use and amethod for their manufacture. The improved particulate material of thisinvention has utility including, but not limited to, use as a proppantin hydraulic fracturing of subterranean formations.

BACKGROUND OF THE INVENTION

In the completion and operation of oil wells, gas wells, water wells,and similar boreholes, it frequently is desirable to alter the producingcharacteristics of the formation by treating the well. Many suchtreatments involve the use of particulate material. For example, inhydraulic fracturing, particles (propping agents or proppants) are usedto maintain the fracture in a propped condition. In hydraulicfracturing, propping agent particles under high closure stress tend tofragment and disintegrate. At closure stresses above about 5000 psi,silica sand, the most common proppant, is not normally employed due toits propensity to disintegrate. The resulting fines from thisdisintegration migrate and plug the interstitial flow passages in thepropped interval. These migratory fines drastically reduce thepermeability of the propped fracture.

Other propping agents have been used to increase well productivity.Organic materials, such as the shells of walnuts, coconuts and pecanshave been used with some success. These organic materials are deformedrather than crushed when a fracture closes under the overburden load.Aluminum propping agents are another type of propping agent that deformsrather than fails under loading. While propping agents such as theseavoid the problem of creating fines, they suffer the infirmity ofallowing the propped fracture to close as the proppant is squeezedflatter and flatter with time. In addition, as these particles aresqueezed flat the spaces between the particles grow smaller. Thiscombination of decreased fracture width and decreased space between theparticles results in reduced flow capacities.

An improved proppant over the materials mentioned above is sphericalpellets of high strength glass. These high strength glass proppants arevitreous, rigid and have a high compressive strength which allows themto withstand overburden pressures of moderate magnitude. In addition,their uniform spherical shape aids in placing the particles andproviding maximum flow through the fracture. While these beads have ahigh strength when employed in monolayers, they are less satisfactory inmultilayer packs. In brine at 250° F., the high strength glass beadshave a tendency to disintegrate at stress levels between 5000 and 6000psi with a resultant permeability which is no better, if not worse thansand under comparable conditions.

Resin coated particles have been used in efforts to improve thestability of proppants at high closure stresses. Sand or othersubstrates have been coated with an infusible resin such as an epoxy orphenolic resin. These materials are superior to sand at intermediatestress levels. However, at high temperature and high stress levels, theresin coated particles, still show decrease in permeability to about thesame degree as silica sand.

U.S. Pat. No. 3,492,147 to Young et al. describes a process forproducing particulate solid coated with an infusible resin. Theparticulates to be coated include sand, nut shells, glass beads andaluminum pellets. The resins used include urea-aldehyde resins,phenol-aldehyde resins, epoxy resins, furfuryl alcohol resins andpolyester or alkyd resins. These particles are used as proppants infracturing operations.

U.S. Pat. No. 4,443,347 also describes a method for propping fracturesin subterranean formations using proppants comprised of sand particleswith a precured phenol formaldehyde resin coating.

U.S. Pat. No. 3,929,191 to Graham et al. discloses a method forproducing coated particles for use in treating subterranean formations.Particles in this method are coated with a resin dissolved in a solventwhich is then evaporated. The patent also discloses the coating may beproduced by mixing the particles with a melted resin and subsequentlycooling the mixture, forming a coating of resin on the particles. TheGraham patent also discloses that the addition of coupling agents to thesystem improves the strength of the resin-substrate bond.

Although resin coated sands have proven satisfactory in numerousapplications, concern exists over their use under high closure stresses.For example, some self consolidating resin coated particles of the priorart do not develop their full strength until the resin coating has curedin the formation. In the event of rapid closure of the fracture, theproppant could be crushed before the resin cured, resulting in decreasedpermeability. The use of dual resin coated particles, such as describedin U.S. Pat. No. 4,585,064, partially alleviates this problem.

As deeper wells with higher closure stress and harsher conditions arecompleted, even higher strength proppants are needed. That need issatisfied by the present invention which provides a dual resin coatedparticle having a reinforcing agent interspersed at the innerresin/outer resin boundary.

SUMMARY OF THE INVENTION

The present invention provides an improved resin coated particlecomprising a particulate substrate, a substantially cured inner resincoating and an outer resin coating, with a reinforcing agentinterspersed at the inner resin coating/outer resin coating boundary.The outer resin may be heat curable, fully cured, or of intermediatenature.

The invention also provides an improved method for treating subterraneanformations comprising placing in the formation a quantity offree-flowing, dual coated reinforced particles. If particles with acurable outer coating are employed, the heat curable particles can becured to form a coherent mass.

The present invention also provides an improved method for producing afree flowing dual resin coated particle. These improved resin coatedparticles are produced by first coating the substrate with a reactiveresin, next dispersing a reinforcing agent at the surface of the firstresin coating and then substantially curing that resin. A second orouter coating of a resin is then coated over the inner resin coating andreinforcing agent.

DESCRIPTION OF THE INVENTION

The present invention can be carried out with any suitable substrate.Choice of the particulate substrate is governed by the propertiesrequired by the particular application. One advantage of the inventionis that conventional frac sand can be rendered superior to the moreexpensive manufactured proppants.

For example, in the oil and gas industry extremely high strengthproppants are needed to hold open formation fractures created byhydraulic fracturing. In such an application, the present invention mayuse spherical glass beads as the particulate substrate. Such beads areavailable commercially in a variety of mesh sizes. For example, UnionCarbide Corporation supplies vitreous, rigid, inert, substantiallyspherical pellets under the tradename UCAR props. Such beads, while ofextremely high strength when employed in monolayers are lesssatisfactory when placed in multilayer packs. These beads when resincoated by the process of this invention and then cured in place yield apermeable mass of higher compressive strength than either the beadsalone or resin coated beads of the prior art. Beads from about 6 toabout 200 mesh are generally used. In extreme environments wherestresses are very high, sintered bauxite, aluminum oxide, and ceramicssuch as zirconium oxide and other mineral particulates may be coated.Particles from 6 to 100 mesh are generally used. (All reference to meshsize of the claims and specification are to the U.S. standard sieveseries).

Also suitable for use as substrates are various organic materials suchas walnut and pecan shells, synthetic polymers such as nylon,polyethylene and other resin particles. Metallic particles such as steeland aluminum pellets can also be coated.

Conventional frac sand is the preferred particulate substrate of theinvention. Silica sand of about 6 to 100 mesh (U.S. standard sieve) isgenerally used. One of the principal advantages of the instant inventionis that frac sand coated by the method of this invention is as strong orstronger than the more expensive proppants described above. Just asimportantly, in conditions where extreme stresses are expected theusable range of such high stress proppants as bauxite and the otherceramics can be extended by following the teachings of this invention.

Resins

Resins suitable for the inner and outer coatings are generally anyresins capable of being coated on the substrate and then being cured toa higher degree of polymerization. Examples of such resins includephenol-aldehyde resins of both the resole and novolac type,urea-aldehyde resins, melamine-aldehyde resins, epoxy resins andfurfuryl alcohol resins and copolymers of such resins. The resins mustform a solid non-tacky coating at ambient temperatures. This is requiredso that the coated particles remain free flowing and so that they do notagglomerate under normal storage conditions. If desired, the resin ofthe outer coating can be fusible to allow cross linking of the resincoated particles during curing. Alternatively, the outer coating can besubstantially cured such that little or no cross linking takes placeupon exposure to downhole conditions. Outer resins of an intermediatecharacter can also be prepared. Such outer resins, while not as reactiveas the typical prior art self-consolidating proppants, still retain adegree of reactivity.

The preferred resins are the phenol-formaldehyde resins. These resinsinclude true thermosetting phenolic resins of the resole type andphenolic novolac resins which may be rendered heat reactive by theaddition of catalyst and formaldehyde. Such resins with softening pointsof 185° to 290° F. are acceptable.

The inner and outer coatings can be formed starting with the same ordifferent resins. For example the inner coating could be produced from aresole and the outer coat from a novolac. However, for practical reasonsthe use of the same resin for both coatings is preferred.

Regardless of which type of resin is employed a coupling agent assubsequently described is preferably incorporated into the resin to beused as both the inner and outer coating during its manufacture. Thecoupling agent which has a functional group reactive in the resin systemis added in an amount ranging from about 0.1 to 10% by weight of theresin. The preferred range is from about 0.1 to 3% by weight of theresin. When using the preferred phenol formaldehyde resins, the couplingagent is incorporated into the resin under the normal reactionconditions used for the formation of the phenol-formaldehyde resin. Thecoupling agent is added to the resin reactants prior to the beginning ofthe phenol formaldehyde condensation reaction.

The preferred resin to be used with the method of the present inventionis a phenolic novolac resin. Particularly suitable is a phenolic novolacresin manufactured by Oxychem under the tradename DUREZ® 24-715. Thisresin has a softening point of 207° to 216° F. When such a resin isused, it is necessary to add to the mixture a crosslinking agent toeffect the subsequent curing of the resin. Hexamethylenetetramine is thepreferred material for this function as it serves as both a catalyst anda source of formaldehyde.

Additives and process steps to minimize storage and handling problemshave been described. For example, U.S. Pat. No. 4,732,920, to Graham andSinclair, which is hereby incorporated by reference, describes theaddition of calcium stearate to prevent sintering and mineral oil toprevent dust problems as well as other additives.

Coupling Agent

The coupling agent to be employed is chosen based on the resin to beused. For phenolic resins, the preferred coupling agents are organofunctional silanes such as aminoalkyl silanes. Gamma-aminopropyltriethoxysilane has given excellent results when used in the amount of0.5% with DUREZ® 24-715 resin.

Reinforcing Agent

A key to the increased strength of the resin coated particles of thepresent invention is the addition of a reinforcing agent in the boundaryregion between the inner and outer resin coatings. The reinforcingagents are added after coating the particle with the inner resin coatingbut before the inner coating is cured. Thus the reinforcing agent isdispersed on and in the uncured resin of the inner coat.

Following addition of the reinforcing agent, the inner resin coat issubstantially cured. A second resin coating is then formed over theinner resin resulting in a high strength particle having the reinforcingagent interspersed the inner resin coating/outer resin coating boundary.As used herein, "inner resin coating/outer resin coating boundary" ismeant to describe the placement of the reinforcing agent resulting fromits addition to the uncured inner resin coating as described. The termis not meant to imply that any or all of the reinforcing agentpenetrates both coatings. Rather the term is used as a convenientshorthand to describe the placement of the reinforcing agent in a mannerthat is believed to enhance the bonding of the outer resin coating tothe inner resin coating and increases the overall strength anddurability of the particle.

Suitable reinforcing agents include the materials known to act asreinforcing agents in typical engineering resins and compositematerials. Common to all suitable reinforcing agents is the requirementthat they be of a particle size calculated to give the requiredproperties. For example, various mineral fillers including fumed silica,silica flour, talc, clays, mica, asbestos, calcium carbonate, calciumsulfate, metals and wollastanite are suitable. The size of suchreinforcing agents is typically less than 300 mesh. Reinforcingmaterials of a fibrous or rod like nature should be less than about0.006" and preferably about 0.002" in length. Of these silica flourground to about 325 mesh, is preferred.

Another type of reinforcing agent with utility in the present inventionare impact modifiers used in engineering resins and composite materials.Examples of such materials include polyisobutylene, ethylene-vinylacetate copolymers, ethylene-propylene copolymers and other rubberymaterials. Also suitable are the so-called core shell impact modifiershaving a rubbery core with a graft polymerized crystalline shell. Toobtain the proper particle size cryogenic grinding of the rubberymaterials is useful.

Coating Process Parameters

The inner and outer resin coatings may be formed by a variety ofmethods. For example, the solvent coating process described in U.S. Pat.No. 3,929,191, to Graham et al., hereby incorporated by reference, maybe used. Other processes such as that described in U.S. Pat. No.3,492,147 to Young et al. describes the coating of a particulatesubstrate with a liquid, uncatalyzed resin composition characterized byits ability to extract a catalyst or curing agent from a non-aqueoussolution. As stated above, the preferred resins for use with the instantinvention are phenol-formaldehyde novolac resins and when using suchresins the preferred coating method is a hot melt coating procedure.Such a procedure is described in U.S. Pat. No. 4,585,064, to Graham etal. which is hereby incorporated by reference. The following is adiscussion of typical coating process parameters using the preferredphenol-formaldehyde novolac resins and the preferred hot melt coatingprocess.

The improved high strength particles of the invention are manufacturedin a multi-step process. In the first step a phenol-formaldehyde resininner coat is formed over the particulate substrate. Second, thereinforcing agent is added, followed by curing of the inner resin. Inthe fourth step an outer coating is formed. The outer coating may thenbe substantially cured or if desired cured to a lesser degree.

Formation of Inner Coating

The first or inner coating of resin is formed on the particulatesubstrate by first coating the heated substrate with aphenol-formaldehyde novolac resin. This coating is carried out bypreheating the particulate substrate to a temperature above the meltingpoint of the particular resin used and high enough to insure that whenhexamethylenetetramine is added to the mixture that the resin issubstantially cured. Substantially cured, as used herein, is to beinterpreted as meaning that the cross linking reaction of the resin issubstantially complete and that at typical downhole temperatures onlyminimal additional curing takes place.

Typically the particulate substrate is heated to 350° to 500° F. priorto resin addition.

The heated substrate is charged to a mixer or muller where generallyfrom about 0.5% to about 5.0%, by weight of substrate, resin is added.The preferred amount of resin based on the weight of substrate is about2%.

After completion of addition of the resin to the substrate, thesubstrate and melted resin are allowed to mix in the muller for a timesufficient to insure the formation of a uniform coating of resin on thesand, usually about 10 to about 30 seconds. After the substrate isuniformly coated with the inner resin, the reinforcing agent is added inan amount from about 0.05% to about 2% by weight of substrate. About0.5% by weight of substrate is preferred. The substrate, resin andreinforcing agent are allowed to continue to mix to disperse thereinforcing agent, usually from about 5 to about 30 seconds.

Following this mixing step from about 5 to about 25%, by weight of theresin, of hexamethylenetetramine is added to the substrate resinmixture. The preferred amount of hexamethylenetetramine is about 13% ofthe resin weight. After addition of the hexamethylenetetramine theentire mixture is allowed to mull for approximately 1 minute. By the endof this time the resin coating on the substrate will be almostcompletely cured. The tumbling mass will be reduced to individual grainsof dry resin coated substrate.

Formation of Outer Coating

After the resin coated sand in the muller has broken into individualgrains and appears dry, the inner coating is completed. From about 0.5%to about 5% of phenol-formaldehyde novolac resin by weight of thesubstrate, is then added to the tumbling resin coated substrate. Thepreferred amount of resin added for the outer coating is about 2% of theweight of the substrate.

The resulting mixture is allowed to mix for an additional period ofabout 30 seconds to about 5 minutes. This time must be sufficient toinsure complete coverage of the resin coated particles with the outerresin coating. Upon completion of mixing, powdered hexamethylenetetramine is added to crosslink the outer resin coating. Generally theamount of hexamethylenetetramine added is from about 5 to about 25%based on the weight of the outer resin coating; the preferred amount is13%. An amount of water sufficient to cool the particles for handling isthen added and the particles discharged from the muller.

If a curable outer coating is desired, the hexamethylenetetramine isadded in water. The amount of water in which the hexamethylenetetramineis dissolved should be sufficient to cool the resin coated substratemixture sufficiently to prevent the complete reaction of thehexamethylenetetramine with the novolac resin. The cooling effect of thewater quench also serves to harden the resin coating. The amount ofwater needed ranges generally from about 1 to 5 gallons per thousand lbsof substrate. Generally, a 10% solution of hexamethylenetetramine isadequate to both disperse the hexamethylenetetramine and sufficientlyquench the reaction.

Following addition of the hexamethylenetetramine water solution, themixture is mulled for an additional 20 to 180 seconds. Again thetumbling mass of resin coated particulate substrate reduces toindividual grains and appears dry. Following this additional mixing, theresin coated substrates is discharged from the muller for standardprocessing such as screening, dust removal, cooling and storage orbagging.

EXAMPLE

The following example is a description of a plant size experimentalbatch of reinforced high strength resin coated proppant. The procedurewas as follows:

1. 1020 lbs of 20/35 mesh sand was charged to a heater and heated to425°-450° F.

2. The heated sand was charged to the muller (mixer), requiringapproximately 15 seconds.

3. 19 lbs of DUREZ® 24-715 resin, modified with 0.5% gamma-aminopropyltriethoxysilane, was added to the sand and the muller, requiring 5seconds.

4. After 15 seconds, 5 lbs silica flour (325 mesh) was added.

5. After an additional 10 seconds, 2 lbs 8 oz dry hexamethylenetetraminewas added to the resin coated sand.

6. After an additional 20 seconds of mulling, the resin coating on thesand was almost completely cured. The tumbling mass of sand was dry andhad been reduced to individual grains.

7. 19 lbs of DUREZ® 24-715, modified as above resin was added to thetumbling sand mass (temperature equals 350°-400° F.). This additionrequired 20 seconds.

8. After an additional 80 seconds, 2 lbs 8 oz of hexamethylenetetraminewas added.

9. After an additional 50 seconds of mulling, the tumbling mass of resincoated sand was quenched with 15 lbs of water. 10 seconds beforedischarge mineral oil (8 fl. oz.) was added as a dust control.

10. The resin coated sand was discharged to a screen conveyor.

FORMATION TREATMENT

The free-flowing, particles as produced by the above method may be usedas proppants, gravel packs or fluid loss agents in hydraulic fracturing.In carrying out a hydraulic fracturing operating a fracture is firstgenerated by injecting a viscous fluid into the formation at asufficient rate and pressure to cause the formation to fail in tension.Injection of the fluid is typically continued until a fracture of thedesired geometry is obtained. A carrier fluid having the proppantsuspended therein is then pumped into the fracture. The temperature ofthe carrier fluid during pumping operations will be low so as to preventpremature curing (if curable) of the outer resin coat. The carrier fluidbleeds off into the formation and deposits the propping agent in thefracture. This process is controlled by fluid loss agents which aresmall aggregate particles which temporarily slow the fluid loss to theformation.

After the proppant is placed, the well is shut in with pressuremaintained on the formation. As the pressure within the fractureapproaches the normal formation pressure, the fracture walls close in onthe proppant and apply an overburden stress thereto. If the outercoating is fusible, the strength imparted by the inner coating maintainsthe integrity of the proppant. At the same time ambient formationtemperature heats the outer resin coating. Initially, the resin fusesand unites at contact areas between contiguous particles or with theformation walls. As the temperature increases the polymerizationreaction proceeds until the resin is cured into an insoluble andinfusible cross-linked state. The pendular regions between adjacentparticles bond the packed particles into a permeable mass havingconsiderable compressive strength.

The amount of such cross linking can be controlled during themanufacturing process. Proppants with outer resin coatings that arefusible and heat reactive can be prepared as can proppants withsubstantially cured infusible outer resins. It is preferred that theouter resin coating be cross linked sufficiently to be substantiallyinert to frac fluids so as to not adversely affect their properties. Theapplication will determine the choice of a curable or cured outercoating. For example, a curable coating may be indicated for gravelpacking, while in fracturing a substantially cured outer coating may bepreferred to prevent interaction with the frac fluid.

A more detailed description of the standard industry practices for theuse of resin coated particles in hydraulic fracturing and gravel packcompletion is disclosed in U.S. Pat. No. 3,929,191 which is herebyincorporated by reference.

Further modifications and alternate embodiments of the invention will beapparent to those skilled in the art in view of this description.Accordingly, this description is to be considered as illustrative onlyand for the purpose of teaching those skilled in the art the manner ofcarrying out the invention. Various modifications may be made in themethod. Applicants intend that all such modifications, alterations andvariations which fall within the spirit and scope of the appended claimsbe embraced thereby.

What is claimed is:
 1. A high strength free flowing particlecomprising:a particulate substrate; an inner coating of a substantiallycured resin covering said substrate; and an outer coating of resincovering said inner coating; and a reinforcing agent interspersed at theinner coating/outer coating boundary.
 2. The particle of claim 1 whereinsaid substrate is silica sand.
 3. The particle of claim 2 wherein saidreinforcing agent is selected from the group consisting of mineralfillers, polyisobutylene, ethylene-vinyl acetate copolymers, andethylene-propylene copolymers.
 4. The particle of claim 3 wherein saidresins of said inner and said outer coating are individually selectedfrom the group consisting of phenol-aldehyde resins, epoxy resins,urea-aldehyde resins, furfuryl alcohol resins, melamine-aldehyde resins,polyester resins and alkyd resins.
 5. The particle of claim 4 whereinsaid resins of said inner and said outer coatings are aphenol-formaldehyde resin.
 6. The particle of claim 5 wherein said resinof said inner coating has a coupling agent reactive with said substrateincorporated into said resin so as to increase the strength of theresin-substrate bond.
 7. The particle of claim 6 wherein said couplingagent is an organo-functional silane.
 8. The particle of claim 7 whereinsaid resin of said outer coating is a phenol-formaldehyde novolac resinhaving sufficient unreacted hexamethylenetetramine incorporated thereinto render said outer coating heat reactive.
 9. The particle of claim 7wherein said outer coating is substantially cured.
 10. A high strengthfree flowing particle comprising:a particulate substrate suitable foruse as a proppant; an inner coating of a substantially curedphenol-formaldehyde resin covering; a solid outer coating of aphenolformaldehyde novolac resin covering; and a reinforcing agentselected from the group consisting of mineral fillers, polyisobutylene,ethylene-vinyl acetate copolymers, and ethylene-propylene copolymersinterspersed at the inner coating/outer coating boundary.
 11. Theparticle of claim 10 wherein the amount of said resin comprising saidinner and said outer coating is each from about 0.5 to about 5 weightpercent by weight of the particulate substrate.
 12. The particle ofclaim 11 wherein said particulate substrate is silica sand.
 13. Theparticle of claim 12 wherein said resin of said inner coating has acoupling agent reactive with said substrate incorporated into said resinso as to increase the strength of the resin-substrate bond.
 14. Theparticle of claim 13 wherein said coupling agent is an organo functionalsilane.
 15. The particle of claim 14 wherein said reinforcing agent isselected from the group consisting of silica flour, fumed silica, mica,talc, wollastanite, clay, polyisobutylene, ethylene-vinyl acetatecopolymer and ethylene-propylene copolymer.
 16. A high strength freeflowing particle comprising:a particulate substrate suitable for use asa proppant selected from the group consisting of silica sand, ceramics,glass, sintered bauxite and aluminum oxide; an inner coating of asubstantially cured phenol-formaldehyde resin covering said substrate,said coating comprising from about 0.5 to about 5 weight percent, byweight of substrate of said particle; and an outer coating of aphenolformaldehyde novolac resin covering said inner coating, said outercoating comprising from about 0.5 to about 5 weight percent by weight ofsubstrate of said particles; and a reinforcing agent comprising silicaflour interspersed at the inner coating/outer coating boundary.
 17. Theparticle of claim 16 wherein the amount of resin comprising said innercoating is from about 0.5 to about 4 weight percent and the amount ofresin comprising said outer coating is from about 0.5 to about 3.5weight percent, each by weight of particulate substrate.
 18. Theparticle of claim 17 wherein said resin of said inner coating has acoupling agent reactive with said substrate incorporated into said resinso as to increase the strength of the resin substrate bond.
 19. Theparticle of claim 17 wherein said coupling agent is an organo functionalsilane.
 20. A high strength free flowing particle comprising:a silicasand suitable for use as a proppant; an inner coating of a substantiallycured phenol-formaldehyde resin covering said sand having anorgano-functional silane coupling agent incorporated therein saidcoating comprising from about 0.5 to about 5 weight percent by weight ofsand of said particles; and an outer coating of a phenolformaldehydenovolac resin covering said inner coating, said outer coating comprisingfrom about 0.5 to about 5 weight percent by weight of sand of saidparticles; and a reinforcing agent comprising silica flour interspersedat the inner coat/outer coat.
 21. The particle of claim 20 wherein saidouter coating is curable.
 22. The particle of claim 20 wherein saidouter coating is substantially cured.